CN107519858A - 一种掺杂稀土元素钇的甲烷化催化剂的制备方法 - Google Patents
一种掺杂稀土元素钇的甲烷化催化剂的制备方法 Download PDFInfo
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- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims abstract description 12
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims abstract description 12
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- PSNPEOOEWZZFPJ-UHFFFAOYSA-N alumane;yttrium Chemical compound [AlH3].[Y] PSNPEOOEWZZFPJ-UHFFFAOYSA-N 0.000 abstract description 5
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Abstract
本发明公开了一种掺杂稀土元素钇的甲烷化催化的制备方法，本发明属于煤制天然气技术领域，其特征为：通过载体的介孔结构改善活性组分与载体相互作用，加入稀土元素钇从而提高催化剂的催化反应活性、稳定性以及抗积炭能力。其制备方法：采用共沉淀法制备介孔钇铝材料，以硝酸钇和硝酸铝为原料，碳酸氢铵为沉淀剂并调节pH值。采用浸渍法制备催化剂，配置一定浓度的硝酸镍溶液，浸渍在载体上，经陈化、干燥和焙烧制得Ni/YAl催化剂。载体的介孔结构增加了NiO的最大单层分散量，加入稀土金属元素钇(Y)有效的阻止NiAl2O4的形成，从而提高了催化性能。同时制备工艺简单、成本低，环境友好，绿色环保。
Description
技术领域
本发明属于煤制天然气技术领域，涉及以一种掺杂稀土元素钇且具备介孔结构的材料为载体制备的甲烷化催化剂。
背景技术
煤制天然气是指将煤经过气化产生合成气(CO、H2、CO2、H2S、CH4、C2H6等)，再经过甲烷化技术处理制得天然气。煤制天然气的能源转化效率较高，技术已基本成熟，是生产石油替代产品的有效途径。甲烷化工艺的两个重要因素是反应器和催化剂。目前两者均得到一定程度工业化应用而甲烷化催化剂的研发相对薄弱，甲烷化是一个放热反应，反应过程中有高浓度的CO参加，在煤气化过程中会含有微量的H2S等气体，因此要求催化剂有良好的热稳定性，较强抗积碳能力，抗毒性强等特点。这都增大了催化剂的研究难度，阻碍了其工业化生产。
甲烷化工艺的催化剂可以按活性组分分为贵金属催化剂和非贵金属催化剂。用于CO甲烷化体系中的贵金属催化剂主要活性组分包括Pd、Pt、Ru、Rh等，非贵金属催化剂主要包括Co、Fe、Ni、Cu基催化剂。Ni基催化剂以其较高的CO转化率、对CH4较好的选择性和廉价易得而成为目前实现工业化生产的甲烷化催化剂。
Al2O3是工业上被使用最为广泛的催化剂载体，传统的Al2O3具有很多优良性能比如较大的比表面积、较为低廉的售价、粒度分布窄、耐热、分散度高；其有较高的水解稳定性以及相对其他载体更容易负载不同的金属物种，是目前工业甲烷化催化剂载体的主要成分。相对于传统的氧化铝有序介孔氧化铝具有更为多种优良的物化性能，其表面电势不同使得不同的金属离子负载更容易，较大的比表面积、较为严整的结构、表面具有酸性中心等特点。目前合成介孔氧化铝的方法主要通过铝源与模板剂相互作用，形成胶状的氢氧化铝，进一步处理后得到介孔氧化铝。
一氧化碳甲烷化催化剂的助剂一般为稀土金属、碱土金属等。助剂本身没有活性，但它的加入可以大幅提高催化剂的活性、抗积炭性、稳定性以及使用寿命，并且可以改变催化剂和载体的表面性能。目前已有一些关于稀土在Ni基甲烷化催化剂中的作用机理报道。作为一种促进剂，稀土兼具电子型助剂和结构型助剂的双重作用。Al2O3的表面呈酸性，当负载活性组分后的催化剂在反应过程中很容易造成积炭失活，所以需要加入稀土元素或碱土金属等添加剂进行改性以提高其热稳定性和改变载体表面的酸性。
发明内容
本发明目的在于制备一种掺杂了稀土元素钇的具有介孔结构的甲烷化催化剂，通过载体的介孔结构改善活性组分与载体的相互作用，加入稀土元素钇改变载体表面的酸性以提高催化剂的催化反应活性、稳定性以及抗积炭能力。
本发明的目的通过以下步骤实现：
载体的制备：以硝酸钇和硝酸铝为原料，碳酸氢铵为沉淀剂并调节pH值。采用共沉淀法制备介孔钇铝材料。将硝酸钇和硝酸铝按一定摩尔比配置成盐溶液。于水浴下搅拌至完全溶解，1mol/L的碳酸氢铵(NH4HCO3)逐渐滴加到混合溶液中，并调节pH＝8左右。滴加完后，反应结束后，继续搅拌陈化，随后经过抽滤，水洗，醇洗，得到白色的前驱体沉淀物。将白色的前驱体沉淀物焙烧得到的载体样品YAl。
催化剂制备：采用浸渍法制备催化剂。配置一定浓度的硝酸镍溶液，浸渍在载体上，经陈化、干燥和焙烧制得Ni/YAl催化剂。
本发明具有以下优点：
(1)载体的介孔结构增加了NiO的最大单层分散量，因此Ni/YAl35催化剂具有更好的CO转化率和更优的产物分布，当反应温度为350℃时，CO转化率97％左右，CH4产率和选择性85％左右。
(2)稀土金属元素钇(Y)加入有效的阻止NiAl2O4的形成，随着Y含量的增加，氧化镍的中温还原峰向高温方向移动，载体的介孔结构有效的改善了氧化镍和氧化铝的作用方式，提高了催化性能。
(3)当氧化镍含量为20％时，20％Ni/YAl35-550℃催化剂具有良好的低温催化性能，当反应温度为400℃时，CO转化率接近100％，CH4产率和选择性98％左右。
附图说明
下面结合附图和实施例对本发明作进一步说明。
图1是实施例1制备催化剂的性能测试图；
图2是实施例2制备催化剂的性能测试图；
图3是实施例3制备催化剂的性能测试图；
图4是实施例3制备催化剂的透射电镜图；
具体实施方式
(1)沉淀法制备介孔钇铝(YAl)载体，具体实施步骤如下：
a.将硝酸钇和硝酸铝按摩尔比3∶5配置成盐溶液，于70℃水浴下搅拌1h至完全溶解；
b.将1mol/L的碳酸氢铵(NH4HCO3)逐渐滴加到混合溶液中，并调节pH＝8左右，滴加完后，反应结束后，继续搅拌3h；
c.将b步骤中反应后溶液陈化24h，再经过抽滤，水洗，醇洗，得到白色的前驱体沉淀物；
d.将白色的前驱体沉淀物经1100℃下焙烧，得到的样品记为YAl35。(其中35代表Y和Al在催化剂中的摩尔比)。
(2)浸渍法制备催化剂，具体实施步骤如下：
配置一定浓度的硝酸镍溶液，浸渍于载体上，室温下静置24h，100℃干燥24h，550℃(以2℃/min的升温速率)焙烧4h最终制的催化剂。
为了进一步理解本发明，下面结合实施例对本发明提供的一种介孔结构的甲烷化催化剂进行说明，本发明的保护范围不受以下实施例的限制。
实施例1：
以硝酸钇和硝酸铝为原料，碳酸氢铵为沉淀剂并调节pH值。采用共沉淀法制备介孔钇铝材料。将硝酸钇和硝酸铝按摩尔比3∶5配置成盐溶液。于70℃水浴下搅拌1h至完全溶解，1mol/L的碳酸氢铵(NH4HCO3)逐渐滴加到混合溶液中，并调节pH＝8左右。滴加完后，反应结束后，继续搅拌3h，然后陈化24h，随后经过抽滤，水洗，醇洗，得到白色的前驱体沉淀物。将白色的前驱体沉淀物经1100℃下焙烧。得到的样品记为YAl35(其中35代表Y和Al在催化剂中的摩尔比)。
催化剂制备：采用浸渍法制备了催化剂。配置一定浓度的硝酸镍溶液，浸渍在载体上，使得NiO含量(质量分数)为20％，室温下静置24h，100℃干燥24h，550℃(以2℃/min的升温速率)焙烧4h最终制的催化剂。将催化剂样品在10MPa下，粉碎后得55-80目颗粒进行催化剂催化活性测试。图1为催化性能测试图。
实施例2：
以硝酸钇和硝酸铝为原料，碳酸氢铵为沉淀剂并调节pH值。采用共沉淀法制备介孔钇铝材料。将硝酸钇和硝酸铝按摩尔比3∶5配置成盐溶液。于70℃水浴下搅拌1h至完全溶解，1mol/L的碳酸氢铵(NH4HCO3)逐渐滴加到混合溶液中，并调节pH＝8左右。滴加完后，反应结束后，继续搅拌3h，然后陈化24h，随后经过抽滤，水洗，醇洗，得到白色的前驱体沉淀物。将白色的前驱体沉淀物经1100℃下焙烧。得到的样品记为YAl35.(其中35代表Y和Al在催化剂中的摩尔比)。
催化剂制备：采用浸渍法制备了催化剂。配置一定浓度的硝酸镍溶液，浸渍在载体上，使得NiO含量(质量分数)为50％，室温下静置24h，100℃干燥24h，550℃(以2℃/min的升温速率)焙烧4h最终制的催化剂。将催化剂样品在10MPa下，粉碎后得55-80目颗粒进行催化剂催化活性测试。图2为催化性能测试图。
实施例3：
以硝酸钇和硝酸铝为原料，碳酸氢铵为沉淀剂并调节pH值。采用共沉淀法制备介孔钇铝材料。将硝酸钇和硝酸铝按摩尔比3∶5配置成盐溶液。于70℃水浴下搅拌1h至完全溶解，1mol/L的碳酸氢铵(NH4HCO3)逐渐滴加到混合溶液中，并调节pH＝8左右。滴加完后，反应结束后，继续搅拌3h，然后陈化24h，随后经过抽滤，水洗，醇洗，得到白色的前驱体沉淀物。将白色的前驱体沉淀物经1100℃下焙烧。得到的样品记为YAl35.(其中35代表Y和Al在催化剂中的摩尔比)。
催化剂制备：采用浸渍法制备了催化剂。配置一定浓度的硝酸镍溶液，浸渍在载体上，使得NiO含量(质量分数)为20％，室温下静置24h，100℃干燥24h，650℃(以2℃/min的升温速率)焙烧4h最终制的催化剂。将催化剂样品在10MPa下，粉碎后得55-80目颗粒进行催化剂催化活性测试。图3为催化性能测试图。
Claims (7)
1.一种掺杂稀土元素钇且具备介孔结构的甲烷化催化剂，其特征在于：
(1)沉淀法制备介孔钇铝(YAl)载体，具体实施步骤如下：
a.将硝酸钇和硝酸铝按摩尔比3∶5配置成盐溶液，于70℃水浴下搅拌1h至完全溶解；
b.将1mol/L的碳酸氢铵(NH4HCO3)逐渐滴加到步骤a所制混合溶液中，并调节pH＝8左右，滴加完后，反应结束后，继续搅拌3h；
c.将b步骤中反应后溶液陈化24h，再经过抽滤，水洗，醇洗，得到白色的前驱体沉淀物；
d.将步骤c中白色的前驱体沉淀物经1100℃下焙烧，得到的样品记为YAl35。(其中35代表Y和Al在催化剂中的摩尔比)。
(2)浸渍法制备催化剂，具体实施步骤如下：
配置一定浓度的硝酸镍溶液，浸渍于步骤(1)所述载体上，室温下静置24h，100℃干燥24h，550℃(以2℃/min的升温速率)焙烧4h最终制的催化剂。
(3)所制催化剂由TEM、催化活性测试装置进行表征，结果见附图。
2.根据权利要求(1)所述的制备掺杂稀土元素钇且具备介孔结构的材料为载体的甲烷化催化剂的方法，其特征在于步骤a所用的原料为硝酸钇和硝酸铝，方法为沉淀法。
3.根据权利要求(1)所述的制备掺杂稀土元素钇且具备介孔结构的材料为载体的甲烷化催化剂的方法，其特征在于步骤b所用的沉淀剂为1mol/L的碳酸氢铵(NH4HCO3)，pH为8左右，搅拌时间为3h。
4.根据权利要求(1)所述的制备掺杂稀土元素钇且具备介孔结构的材料为载体的甲烷化催化剂的方法，其特征在于步骤c中陈化时间为24h。
5.根据权利要求(1)所述的制备掺杂稀土元素钇且具备介孔结构的材料为载体的甲烷化催化剂的方法，其特征在于步骤d中样品的焙烧温度为1100℃。
6.根据权利要求(2)所述的制备掺杂稀土元素钇且具备介孔结构的材料为载体的甲烷化催化剂的方法，其特征在于焙烧温度为550℃，升温速率为2℃/min，焙烧时间4h。
7.根据权利要求(3)所述的制备掺杂稀土元素钇且具备介孔结构的材料为载体的甲烷化催化剂的方法，其特征在于TEM图见附图，催化活性见附图。
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